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COMHISSARIAT A L'ENERGIE ATOMIQUE

CENTRE D'ETUDES NUCLEAIRES DE SACLAY CEA-CONF ~ 8773

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F9I191 GIF SUR YVETTE CEDEX

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LABORATORY AND PLANT INVESTIGATIONS ON DECOMPOSITION

PRODUCTS OF MORPHOLINE IN THE SECONDARY SYSTEM OF FRENCH PWR

UAUVOIS, V . ; LAMBERT, I . CEA CEN Soclay, 91-Git-sur-Yvette ^France;

IRDI

DESM0ULIN5, D.; NORDMANN, F. Electricit de Fronce, 93-Soint-

Denis

Communication prsente : 4 . International conference on water

chemistry of nuclear reactor systems
Bournemouth lUK;
13-17 Oct Iy86
V. DAUVOIS, D. DESMOLLINS, I. LAWSERT. F. NRDMANN

Laboratory and plant tests have been carried out on French PWR operating with morpholine treatment.
Morpholine decomposition products are one significant origin (but not the only one) of organic acids in the
secondary system. Acetic and formic acids are reported to be responsible for a cation conductivity increase
of about 0.2 M S/cm at steam generator blowdown. On units with a deaerating tank in the feedwater train,
organic acids are partially eliminated and cation conductivity is lower in the secondary system. On a unit
unvoluntarily polluted with oil, a synergistic effect between contamination -oxygen- morpholine. on organic
acid content has been demonstrated.

1. INTRODUCTION plant design, is represented on Table 3.

Due to the corrosion-erosion damage which occured
in several pipes of the secondary system of French Table 1. Implementation of morpholine treatment in
?WR, a series of countermeasures have been taken EDK PWR plants
(ref. 1). Since the materials modifications required
several years to be completed, the choice of a
particular chemical treatment against the corrosion- PLANT UNIT DATE
erosion phenomenen was decided by Electrit de
France in June 1983. It consists of a pH increase Fessenheim 1-2 Sept. 4 July 1983
in the water-liquid phase where corrosion-erosion
takes place. In order to get a sufficiently high pH Bugey 2-3-4-5 Sept. to Nov. 1983
t operating temperature with ammonia, the Tricastin 1-2-3-4 Nov. 4 Dec. 1983
feedwater must be treated with a high concentration
which is not compatible with copper alloy tubing of Dampierre 1-2-3-4 October 1984
some low pressure heaters and condensers. Thus, Blayais 1-2-3-4 June 1984 a
another chemical treatment has been selected, Oct. 1985
based on morpholine (and hydrazine) additions. It
has been applied on all the units with copper alloys St-Laurent B I-2 Jan. 4 June 1981
(all of the river water cooled plants) and also on Chinon B 1-2 Sept. 4 Aug. 1984
some of the sea-water cooled copper-free units. The
date of switching from ammonia to morpholine Cruas l-2-3-4 Feb. to Oct. 1984
treatment is shown on Table 1. Paluel I-2-3* June 1984,
The six units of GRAVELINES are operating with Sept. 1984,
ammonia. Table 2 indicates the chemistry specifica- Sept. 1985
tion chosen for the moipholine treatme.it. It must
be mem ionned-that none of EDF PWR has conden- St-Alban 1 August 1985
sate polishing plant. Flarnanvillt 1 December 1985

2. CATION CONDUCTIVITY INCREASE * Units with morphoiine treatment since starting-up

When the decision was taken to switch most of Table 2. EDF chemistry specification for morpho-
French PWR to morpholine treatment, a past expe- line treatment
rience was already gained with this amine during a
few fuel cycles. Comparative results had shown a
cation conductivity increase at steam generator SAMPLING POINT PARAMETER VALUE
blowdown with morpholine. Consequently, a large
programme was initiated to study decomposition pH at 2 5 ' C 9.1 to 9.3
products of morpholine, both in laboratory and in
operating plants. For these ones, investigations have FEEDWATER Morpholine ~>, 4 ppm
been conducted first on Tricastin unit 4, specifical- Ammonia fa)
<0.3 ppm N H +

ly polluted by organic species, and then in the

moisture separator reheater drain of air.iost all the
other PWR units. MAKE-UP WATER Morpholine > ppm
The cation conductivity inctease at steam generator (a) Ammonia comes only from hydrazine thermal
blowdown of units which had been switched from decomposition
ammonia to morpholine treatment, is now confirmed.
The increase range, which is different according to
V. DALVOIS, D. DtSMOLLlNS, I. L A M B E R I , F. NORDMANN
Table 3. A increase with motpholine compare! to NH
French Design Average cation conducti-
PWR series specificity viiy increase r* lge at
steam generator
blowdown
CP0-CP1 No rieae-
r a nng 0.15 uS/cm
tank
CP2 Deae ra (0 to 0.1) few compa
ting tank rative data
3. MORPHOLINE INFLUENCE ON CATION
CONDUCTIVITY-LABORATORY INVESTIGATIONS
The action of dilute solutions of pure and thermo-
lyzed morptoline on cation conductivity has been
investigated with laboratory resins.
3.1 Tested solutions
All the solutions are prepared with pure chemicals
and very pute water, the conductivity of which is
lower than 0.1 uS/cm, by passing water thtough
active charcoal, mixed beds and 0.22 um filters.
Solutions ate handled under an inert gas blanket.
n
The concenttation of CO, < morpholine was deter
mined by gas chromatography and found to be
lower than 100 ug/kg of amine. So, carbon dioxide
pollution coming from morpholine is negligible in a
secondary water containing 4 ppm m .rpholine.
Nevertheless, a dilute solution of morpholine is
found to absorb gaseous CO, faster than an
ammonia solution of the same molar concentration.
3.2 Method of thermolysis
Free from oxygen and catbon dioxide dilute solu
tions of morpholine (0.1 or 0.01 M) are thermoly-
ted at 300 C under an inert gas blanket, in a
titanium autoclave, equipped with a magnetic
stirrer. After cooling down the autoclave, the
solution is drained under inert atmosphere, into a
tinted glass, since light exposute and oxygen were
found to change tne composition of thermolyzed
morpholine solution: at room temperature.
3.3 Solutions of pure morpholine
In order to see if dilute solutions of rr.orpholine
could react with cation exchange resins and contri
bute to cation conductivity ( A ), we measured the
conductivity of several solutions containing Na CI,
Na HC0, , with or without morpholine, and after
having been passed through a bed of SO ml sulfonic
acid cation exchange resin (duolite C 20 H) at a
flow rate 10 vol/vol/h. Th measured A* of pure
water, in these tests is 0.14 uS/cm at 21* C. For
further A calculations of the various tested
solutions, it is assumed that this A * blank corres
ponds to 17 ppb of Na CI, using usual A ' calcula
tions. Results of measured and calculated A "
aftet the resin are shown on Table 4.
A gcod agreement between measuted and calcula
ted A* values is noted for solutions with or
without morpholine. Whatever the composition of
the solution is, there is no specific action of pure
morpholine on A*. The amine is fully exchanged
and does nor contain acids.
Table 4. Laboratory results on cation conductivity
ol various morpholine solutions
Solutions A* uS/cm at 21* C
Water measured calculated
Nothing 0.14 - 0.01 assumed
0.14
45 ppb Na CI 0.42 - 0.02 0.44
45 ppb Na CI *
10 ppm moiphol ine 0.42 t 0.02 0.44
45 ppb Na CI
1C0 ppb CO, 0.60 - 0.02 0.62
45 ppb Na CI
10 ppm morphol ine 0.60 - 0.02 0.62
100 ppb CO,
45 ppb Na CI <
500 ppb CO, 0.98 - 0.01 1.02
45 ppb NaCI -
10 ppm morpholine 0.98 - 0.01 1.02
500 ppb CO,
3.4 Solutions of thermolyzed morpholine
A 0.1 VI morpholine soluncn was thermolyzed
during 48 hours, with the cautions described in
3.2. After passing this solution over the resin, in
the same way as pure morpholine solution in $ 3.3,
the chemical characteristics are the following
. pH at 21 C : 3.4
. acidity (except C0 ) : 3.68 x 10 N
2
. conductivity at 21 C : 139 u S/cm.
This clearly demonstrates that passing a thermoly
zed morpholine solution through a cationic resin
leads ro an acidic solution which may come either
(torn the thermolyzed solution itself, ot from its
reaction with the resin.
If diluted by a factor of 870, in order to get a
10 ppm morpholine solution, the measured A*
becomes 1.66 p S/cm, instead of 0.16 u S/cm. This
difference, as well as pH -acidity comparison on
the non- diluted solutions indicates the presence of
weak acids.
4. ANALYSIS OF MORPHOLINE DECOMPOSITION
PRODUCTS
Several solutions of dilute morpholine have been
tnermolyzed at 300 C under an inert gas blanket
during 4 up to 21 days, in order to identify acidic
ions.
4.1 Solution treatment before acids analyses
Before anions analysis by ion chromatograpny, the
thermolyzed solution is treated in the following
way, so as to remove ethylene glycol and aldehydes
which might poison the chromatography columns ;
. the solution is passed thtough a strong
cationic resin bed (duolite C 20 H) with a
flow rate of 10 vol/vol/h
. the pH, conductivity and acidity of the
solution ate measured
. in order to fix anions, the solutions are
passed through a weak anionic resin
(duolite A 561) at a flow rate of 10-14
vol/vol/h ; the weak anionic exchanger was
selected for its ability to both fix all ilte
V. DAUVOIS. D. DESMOULINS. I. LAMBERT. F. NORDMANN

anions from the acidic solution and Table 5. Analyses of morpholine, thermolyzed at
release them easily with dilute sodium 300 C
hydroxide
. the anionic resin is washed wirh 25 times Test Thermolysis Initial mor- X of
its volume of deionized water in order to number duration pholine remaining
remove the eventually adsorbed poisons days content basicity
(flow rate of 12 vol/vol/h) mole/kg
. the anions are eluted with \ a OH 0.4 \
(12 times the resin volume, flow rate of 1 4 0.10 68
6 vol/vol/h) and analyzed by HPIC (high
performance ion chromatography) and 2 "4 1.00 10 88
HPICE (high performance ion chromato 3 4 1.04 10 85
graphy exclusion)
All the previous steps are carried out with resins 4 8 1.00 10 82
and solutions protected from oxygen, carbon dioxide 5 8 0.98 10
and light. The "efficiency" ot the treatment, befote
chromatography analyses, is evaluated in each case 6 21 0.86 10"
by comparing the amount of anions found by the
analysis to the acidity of the solution obtained after
passing the termolyzed solutions through the cano Test Characteristics of the acidic solution at
nic resin. Howewer, the departure from 100 % can number 21* C
be due either to a non complete recovery or to
non detected anions. acidity eq/kg pH A* u S/cm

4.2 Titration method for bases 1 4.7 10 " 3

3.38 166
With the same cautions as those taken for the 2 5.3 10 -* 4.0 51
analysis of acid species, the thermolyzed solution
of morpholine is passed through a strong anionic 3 5.0 10 ~* 3.9 53
resin (duolite A 101 OH) able to fix anions and 4 8.4 10 ~* 3.63 60
organic compounds having an anionic function.
Basicity and pH of the resulring solutions are 5 7.6 10 ~* 4.09 59
measured. 6 1.2 10 " 3
4.10 55
4.3 Results and discussions
Table 5 gives
. the percentage of remaining basicity Test Results of the anionic chromai eg raphy
. the characteristics of the acid solutions number acids treatment HCOO" CHjCOO" S 0 * 4

obtained by passing the thermolyzed

morpholine solution through a cationic "efficiency" * X (a)
resin
. the "efficiency" of the treatment of the 1 78 18.4 58 1.46
acidic solution 2 96 49 45 1.96
. the percentage of formates, acetates and
sulfates related to the normality of the 3 94 54 38 1.95
acidic solution. 4 92 22.2 69 0.62
The column % HCOO" covers both formate HCOO"
and glycolate CH, OH-COO" ions of same retention 5 91 23.5 66 0.84
time. The total is computed according to formate 6 88 10.8 77 0.58
calibration ciyve, on HPICE.
CO. is detected by gas chromatography after (a) X HCOO" represenrs formate glycolate.
acidification.
Oxalates C, 0 . are also detected, but at a very . the percentage of remaining basicity is
minor concentration. Glyoxylates CHO-COO" are higher for the less concentrated morpho
lower than the detection limit. line solution. Condensation reactions
The pH of the remaining basic solution is higher might occur with the 0.1 M solution ;
than the one of the initial fresh solution proving thus the 0.01 M solution was preferred
the presence of bases stronger than morpholine, for further tests
. the sulfate concentration is nearly pro
such as ammonia, diethanolamine and monethanola-
portional ro the amine inirial rnncrnrta
rriinc, coming from nv>rpholine thermal deton.oosi-
lion ; sulfate comes from degradation of
tion (S 4.4).
the sulfonic cationic resin by thermolysis
Fig. 1 shows the evolution of acidity, acetate and
decomposition products (likely non-ionized
formate concentrations versus decomposition time
ones such as aldehydes)
of a 0.01 M morpholine solution.
. the percentage of formate is higher for
4.4 Morpholine concentration influence the 0.01 M than for the 0.1 M solution.
The thermolysis comparison of a 0.1 and 0.01 M This could be attributed to the effect of
morpholine solution, during four days allows to say either condensation between decomposi
that : tion products or further decomposition
. the aciditv is nearly proportional ro initial into carbon dioxide and hydrogen.
morpholine concentration
V. DAUVCIS. D. DES.VtOLLINS, I. LAMUERT, F. NORDWANN

anionic concentration sure rehearer. The main analytical results noticed

(eq/l) during rhe polluted fuel cycle are the following.

total acsraina *
aciditv

^, acetate

- l~**-*C*. * , s c

formate r - * i t i ' t 3* j

" " Decomposition

duration (days) 'J*. it*.

Fig. 1. Evolution of decomposition producrs of

0.01 M morpholine solution, at ?00 C,
versus time.

4.5 Time exposure influence First step : HYDROLYSIS

The comparison of a 0.01 VI morpholine solution
thermolysis at various decomposition durations 1
WO.:* eawsir; ^oour-,
indicates that (cf. Table S) :
. the formate percentage versus thermolysis
duration decreases and may be due to the
same effect as explained in S 4.4 for
formate
. the acetate percentage versus time increases
. the sulfate percentage versus time decreases

4.6 Mechanism of morpholine decomposition

Theoritical investigations supported by laboratory
experiments allow to propose the following thermal
decomposition schema of morpholine, in two steps :
. hydrolysis of morpholine into other amines
and glycol
. oxidation into aldehydes and organic acids I*T c-8
The second step can take place at high tempera SL'OIVLC CO
ture, in preseAce of a metallic catalyst (copper,
iron oxide, e t c . ) .

5. INVESTIGATIONS ON A POLLUTED UNIT NO ^ *

Th; first large investigations on French P'.VR opera
ting with morpholine have been conduced on
Tricastin 4 where the cation conductivi'y (A*)
reached 1.3 uS/cm at steam generator blowdown
and 2.4 uS/cm at moisture separator reheater
(MSR) drain. Such a high conductivity appeared
during the first morphoiine treatment fuel cycle,
and several difficulties rose on evaluation of
morpholine specific contribution :
. many cooling water inleakages occured into
the secondary system
. acetate was the main contriburor to A * at
MSR drain but not at the steam generator
(SO blowdown.
However, the high detection limit at that time did
not allow to evaluate accurarely acerate contribu
tion at SG blowdcwn. During trie refueling ouf.ige
following that chemically disturbed fuel cycle, a
contamination bv oil w.is discovered in a low pres
Second step : OXIDATiON
5.1 Power influence
The effect of the percentage of nominal electric
power of the unit on A* all along the secondary
system is shown on Table 6 : a power increase
leads to a A increase.
5.2 Morpholine concenrration effect
Tile influence of morpholine concentration on A *
values have been compared in Tricastin 4, where the
oil pollution was discovered, and in Tricastin 1,
where the switch to rrorpholine treatment had not
been associated to a drastic A" increase. The
values of Table 7. all ar 100 \ power operation.
V . DAUVOIS, D. DESMOLLINS, 1. LAMBERT. F. NORDMANN

show that the A* increase with morpholine concen

3/*\
tration occurs only on the polluted unit.

Table 6. Effect of power on A at Tricastin 4

PWR unit in presence of an oil pollution.

X* SG U )
X* steam V)

ill
Power A* MSR
% u S/cm p S/cm p S/cm

30 0.50 0.15 0.65 7.5

100 1.3 0.50 2.4 5.5

(a) 1 : cation conductivity

SG : steam genetatot
Fig. 3. Circulation loop of acetic acid in the secon
(b) MSR : moisture separator reheater drain.
dary system.
Table 7. Effect of morpholine concentration on A'
5.4 Oxygen influence
at Tricasttn
Still on Tricastin unit 4, a A* increase at SG blow-
+
X " MSR Morpho down has been noticed during an incidental air in-
Unit Oil A SG A steam
leaJcage at the condensate pump inlet while the
pol u S/cm u S/cm u S/cm line
plant was operating at 100 % power, with morpho
lution ppm
line tteatment. Comparative tests have been conse
quently petformed on two units of Tricastin,
4 YES 2.0 0.9 4.2 7
. unit 3 : morpholine treatrrent, no specific
1.3 0.6 2.5 2
pollution
. unit 4 : morpholine treatment oil pollution
1 NO 0.5 5
in otder to evaluate the effect of oxygen on
0.5 12
_ the oxidation step of decomposition products
of morpholine, leading to organic acids, as
5.3 Acetate content postulated from laboratory tests
The ptesence of acetate in the secondaty system _ on oil thermal decomposition products.
corroborates the laboratory investigations which The results, Fig. 4 a and b, and laboratory analyses
demonstrate that morpholine decomposition products on organic acids allow to conclude that, in both
include acetate. Acetate content all along the se cases, acetic acid concentration in MSR drains is
condary system of Tticastin 4, during the period ot about twice at the end of the air ingress test, as
oil presence in reheater, is represented on Fig. 2 compared to initial value, and that acetate ccmes
from the oxidation of otganic species.
The air inleakage did not affect the fotmic acid
content, about 20 ppb in unit 3 and 60 ppb in unit
4, during all the test, at MSR drains.

5.5 Carbon dioxide

OE h fppL
m L}'
Fig. 2. Arrrar* rnnrifnrrsjrinn (in ppb) in the secon
daty system of Tticastin 4, with morpholine,
ill pie-sein.e of Aft oil pollution.
A recirculating loop of acetic acid/acetate in the
secondary system is noticeable on Fig. 3 and exp
lains the acetate difference between MSR outler
and inlet. It gives rise to an accumulation of ace
tate, particularly significant in MSR dtain. Some
hypothesis, rill under investigation, are postulated
to explain why, on one hand, acetate is mostly
directed toward steam and quite not in SG liquid
blowdown, and on the othet hand acetate concen
trates in thr water liquid drain of MSR.
Carbon dioxide investigations during these specific
tests as well a duting other operating phases,
clearly evidenced that CO, is not the main contri
butor to cation conductivity increase in the secon
dary system, except in the condensate water during
air ingress.
6. PWR PLANT SURVEY
Facing the high amount of otganic acids observed on
(he specifically polluted unit of Tricastin, EDF
decided to carry out complete anion measurements
in the MSR drains of 30 PWR unit;. Thi? <ampling
point has been selected according to the fact that
organic acids recirculate in (he loop represented on
Fig. 3 and that MSR drain is the secondary system
part where acetic acid is present at (he highest
concentration. Comparisons have been conducted on
several types of units in order to evaluate the
ir.f'uc: =ss of
. morpholine treatment versus ammonia one
. the presence of a deaerating tank
The organic acid results are gatthered on Table 8.
V . DALVOIS, D. DESV.011..XS, !. LAMBERT. F. NOKDMANN

origin of organic acids in the secondary

* - Cation conductivity (uS/cm)
system of PWR, acetate being apparently
the main acid among dcomposition products
. however, morphoiine is not the only origin
MSR of otganic acids ; non ionized organic com-
pounds are introduced into the system via the
make-up water and then are thermally de-
SC BLOVvDOAN composed into ionic compounds
. the deaetating tank has a grear efficiency
for elimination of acetic acid, and to a less
extent of fotmic acid from the secondary
"i 1 1 !>aaaa system.
Hours
Table 8. Organic acids in MSR drains of 30 French
Cation Conductivity Evolution
PWR units
.!. Oxygen (ppb)

a
PVVR Design AVT Acetate Formate
seties specificitv reagent ppb ppb
(b)

i i CPO No deaera- Morpho-

iine
60 17
CPl ting tank
-sr (a)
Hours CPl No deae ra- Ammo- 33 4
Oxygen concentration in condensate watet
ting tank nia
b) CP2 Deaerating Morpho- 9 8
V Cation conductivity (uS/cmj tank iine
MSR Paluel New unit Morpho- 195 ^4
iine

30
units 60 11
ave-
rage

(a) Tricastin 4, specifically polluted, is not included

"***tas>a' in the average values of this table
Houts (b) F.DF-PWR units does not have condensate
Cation Conductivity Evolution
polishing plants.

Oxygen 7. CONCLUSION
Ippb) Since 1983, the all volatile motpholine treatment is
applied to almost all of the French PWR secondary
water, in order (o decrease corrosion-erosion phe-
nomenon. The large programme which has been
performed in laboratory and in operaring units
allows to conclude on the following points.

7.1 The switch from ammonia t o morphoiine treat-

Oxygen concentration in condensate water
ment implies an average cation conductivity increase
of 0.2 uS/cm at steam genetatot blowdown. Plant
Fig- 4. Air ingtess test on Tticastin plant investigations indicate the presence of organic acids
a) unit 3 . no specific pollution in the secondary system but low amount of carbon
b) unit 4 : oil pollution. dioxide which is not the main contributor to the
ration rondurriviry values.
Acetate level is much lower on rhe CPl than on
CPl and CPO units. The deaerating tank seems to
7.2 The laboratory tests confirmed that the cation
be an import"./.! factor for elimination of volatile
conductivity increase is nor due to morphoiine
otganic acids (or aldehydes). In case of morphoiine
impurities but to thermal decomposition products.
treatment, the equilibrium concentration in CP2
Experimenrs on 0.01 M morphoiine solutions, after
units, as compared to CPl, is respectively 7 times
8 days of thetmolysis at 300" C have been carried
lower for acetate and twice lower for formate. The
out. The remaining basicity i; S2 "i of ir.itii! <_"'-
influence of morphoiine treatment is shown by
tion. The acid species concentration is of 8.10"
comparing CP0-CP1 units, of same design, with the
eq/kg, i.e. (* IS of initial amine content.
two different AVT reagents. Acetate and fotmate
are respectively 2 and 4 times lowet with .immoma. The main acids ate a c e t i c , fotmic and glycolir.
Thus, it can be said that Only sulfuric acid comes ftom the degtadation of
the cationic resin by concentrated decomposition
. motphohne rreatment is one significant
V . DAUVCIS. D. DESMULINS, I. LAMBtRT, F. NORDMANN
products ; however, in a secondary system of PWR
plant, the low concentration ot these compounds
may not induce sulfate release from resins.
7.3 On operating units, the decomposition schema
has also been evidenced, and the oxidation step
confirmed by higher organic acid concentration
wnen oxygen is added via condenser air ingress.
7.4 On a unit unvoluntarily polluted with oil, a
synergy between morpholine. oxygen and this
organic pollution led to larget amounts of organic
acids (particularly acetic acid). Fig. 5.
f M situ ' secondary water chemistry, nor any degradation of
ICOnrAMMMtlON
Fig. 5. Synergy of organic acid generation in PWR
plan'.
7.5 The feedwater deaerating tank is efficient for
elimination of volatile organic acids from the
secondary system. With morpholine treatment,
acetate content is 7 times iower on units with
deaerating tank, than on the other ones.
7.6 Even though organic acids, mainly acetate and
fotmate, are observed at significant concentrations
in moisture separator reheater drains with morpho-
line treatment, their presence is also noticed with
ammonia treatment. Thus, a programme has been
initiated to evaluate potential corrosion of organic
acids on materials, particularly on steam genetatot
tubes. However, up to now, several Ftench units
have been operated for some years with morpholine
treatment and did not exhibit any type of steam
generator alloy 600 tube corrosion due to the
the tutbine which could be due to the presence of
organic acids in the steam.
Acknowledgment
This wotk is part of a CEA, EDF. Westinghouse
and Framatome R 4 D programme. We tank the
other parties for permitting this publication.
REFERENCE
l. MARCEAU J., bERGE Ph., MALHERBE C ,
TALLEU V.
Cotrosion-erosion in Ftench PV.R secondary cycles,
Ametican Power Conference, April 1984.